Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono(6‐O‐p‐tolylsulfonyl)‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition re...Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono(6‐O‐p‐tolylsulfonyl)‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy (ROESY), ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess (ee) in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using (S)‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl (pH 7.5).展开更多
Aim To prepare and characterize the QURC-HP-β-CD inclusion complexes and investigate the thermodynamic parameters of the process. Methods QURC-HP-β-CD inclusion complexes were prepared by the grinding method. The eq...Aim To prepare and characterize the QURC-HP-β-CD inclusion complexes and investigate the thermodynamic parameters of the process. Methods QURC-HP-β-CD inclusion complexes were prepared by the grinding method. The equilibrium inclusion constants and thermodynamic parameters were determinated by phase solubility analysis. Dissolution tests were performed to study the dissolution rate of inclusion complexes. The formation of inclusion complexes was confirmed by differential scanning calorimetry ( DSC), infrared spectroscopy (IR) , powder X-ray diffractometry (PXRD) and scanning electron microscopy (SEM). Results The aqueous solubility of quercetin was greatly increased ( about 37 folds) by inclusion technique, and the initial dissolution rate was markedly improved (10 folds) in the first 5 min. The results of DSC and SEM photographs showed that quercetin crystal disappeared in inclusion complexes, which indicated the formation of new phase. FT-IR spectra showed that the carbonyl quercetin crystal grinding method. absorption band of quercetin was shifted. PXRD showed that the diffraction peak of disappeared. Conclusion QURC-HP-β-CD inclusion complexes are produced by the The solubility of quercetin is improved by the inclusion technique.展开更多
With LiAc-2H2O as Li precursor,pure olivine phase LiFePO4/C was synthesized at a relatively low temperature(650 ℃) and short sintering period(4 h) by molten salt carbothermal reduction method.Scanning electron mi...With LiAc-2H2O as Li precursor,pure olivine phase LiFePO4/C was synthesized at a relatively low temperature(650 ℃) and short sintering period(4 h) by molten salt carbothermal reduction method.Scanning electron micrograph shows that particle size of the product is about 1μm,smaller than that of the sample synthesized with Li2CO3 as Li precursor.Electrochemical measurements prove that LiFePO4/C obtained from LiAc-2H2O shows high capacity.The initial discharge capacities are 148 mA-h/g at 0.5C rate and 115 mA-h/g at 5C rate,respectively.After 50 cycles,the capacity retention ratios are 93% and 89% at 0.5C rate and 5C rate,respectively.展开更多
ObjectiveThe study aimed to explore the factors regulating carotenoid accumulation in flesh color. MethodA loquat mutation (red-or orange-fleshed plant emerged a bud mutation of white-flesh in trunk) was used as mat...ObjectiveThe study aimed to explore the factors regulating carotenoid accumulation in flesh color. MethodA loquat mutation (red-or orange-fleshed plant emerged a bud mutation of white-flesh in trunk) was used as material; HPLC analysis of β-carotene content was conducted. ResultThe β-carotene concentration in the flesh of wild and mutant types was 60.9 and 4.6 μg/g fresh weight, respectively. According to the conserved regions of genes from rose family genome, carotenogenic gene fragments in wild and mutant types were obtained. No nucleotide variation of the carotenogenic gene fragments was observed between wild and mutant genome. Real-time quantitative polymerase chain reaction (Q-PCR) was compared and one carotenogenic gene, β-ring hydroxylase (HYB) were considerably suppressed in mature mutant loquat fruits compared with that in wild. The other six carotenogenic genes were also expressed but the expression patterns appeared to be not correlated with the amount of β-carotene concentration in wild loquat flesh. ConclusionThe mutant whitish loquat lacks the ability to synthesize β-carotene because of the transcriptional down-regulation of carotenogenic gene HYB.展开更多
We have designed and prepared β-cyclodextrin (β-CD)-functionalized multi-walled nanotubes (MWCNTs-g-CD) for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effec...We have designed and prepared β-cyclodextrin (β-CD)-functionalized multi-walled nanotubes (MWCNTs-g-CD) for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effect of combining MWCNTs with β-CD led to a remarkable increase in the performance of the MWCNTs-g-CD for the catalytic oxidation of cinnamaldehyde, which exhibited 95% cinnamaldehyde conversion and 85% selectivity to natural benzaldehyde with a short reaction time of 10 rain. The MWCNTs-g-CD also exhibited outstanding recyclability with good stability, showing no discernible decrease in their catalytic activity over five reaction cycles.展开更多
Aim To investigate the combined effect of hydroxypropyl-β-cyclodextrin (HP-β-CD) and media pH on the solubility of prostaglandin E1 (PGE1) and construct a theoretical equation for the drug solubility as a functi...Aim To investigate the combined effect of hydroxypropyl-β-cyclodextrin (HP-β-CD) and media pH on the solubility of prostaglandin E1 (PGE1) and construct a theoretical equation for the drug solubility as a function of HP-β-CD concentration and media pH. Methods The solubility of PGE1 under different pH conditions was determined. Then, the drug solubility in different concentrations of HP-β-CD acidic or pH neutral solutions was measured, respectively. Finally, a theoretical solubility equation for the drug as a function of HP-β-CD concentration and media pH was deduced and confirmed in experiment. Results PGEs was solubilized by HP-β-CD or by increasing media pH. The drug solubility as a function of HP-β-CD concentration was found to follow the AL-type complexation model in acidic or neutral pH media, suggesting that both the ionized and neutral drugs form 1:1 molecular ratio complexes. Conclusions The solubility of PGE1 may be improved by increasing media pH or by using HP-β-CD as a solubilizer. HP-β-CD and media pH can produce combined effect on the solubility of PGE1. The deduced equation for the drug solubility in this study effectively characterizes the roles of HP-β-CD and media pH in determining total solubility of the drug.展开更多
A new capillary gas chromatography stationary phase, monokis (2,6 di O benzyl 3 O propyl (3’)) hexakis(2,6 di O benzyl 3 O methyl) β CD bonded polysiloxane, was synthesized. It ex...A new capillary gas chromatography stationary phase, monokis (2,6 di O benzyl 3 O propyl (3’)) hexakis(2,6 di O benzyl 3 O methyl) β CD bonded polysiloxane, was synthesized. It exhibited separation abilities to disubstituted benzene isomers and some chiral solutes. It was also found that the polarity of CD derivatives can be lowered both by chemically bonding it to polysiloxane and by diluting it in polysiloxane. The separation abilities of the polysiloxane anchored CDs (SP CD) are higher than that of the unbonded CDs (S CD) and the diluted S CD at lower column temperature. Hydrosilylation reaction is one of the best methods to lower the operating temperature of CDs.展开更多
Some homological properties of R-modules were investigated by matrices over aring R. Given two cardinal numbers α, β and an α x β row-finite matrix A, it was proved thatExt_R^1(R^((α))/R^((β))A, M) = 0 if and on...Some homological properties of R-modules were investigated by matrices over aring R. Given two cardinal numbers α, β and an α x β row-finite matrix A, it was proved thatExt_R^1(R^((α))/R^((β))A, M) = 0 if and only if M_α/r_(M_α)(R^((β))A) ≈ Hom_R(R^((β))A,M) ifand only if r_(M_β)l_(R^((β)))(A) = AM_α. Thus, the notion of (m,n)-injectivity was extended.Moreover, ( α, β) -flatness was characterized via annihilators of matrices, factorizations ofhomomorphisms as well as homological groups so that (m, n)-flat modules, f-projective modules andn-projective modules were consolidated under the notion of (α, β)-flat modules. Furthermore, acharacterization of left R-ML modules and some equivalent conditions for R^((β)) to be left R-MLwere presented. Consequently, the notions of coherent rings, (m, n)-coherent rings and π-coherentrings were consolidated under that of (α, β)-coherent rings.展开更多
Effects of fish oil on β-adrenoceptors as well as the activity of adenylate cyclase (AC) on rat myocardial membrane were investigated.Supplementation with fish oil had no significant effect on basal activity of AC on...Effects of fish oil on β-adrenoceptors as well as the activity of adenylate cyclase (AC) on rat myocardial membrane were investigated.Supplementation with fish oil had no significant effect on basal activity of AC on myocardial membrane whereas it could markedly inhibit the AC activity stimulated by isoproterenol (ISO). Radioligand binding assays showed that supplementation with fish oil had no effect on Bmax and Kd, compared with saline control. However, supplementation with sheep oil could markedly reduce both the Kd and Bmax, compared with saline control. And the Kd of sheep oil group was greatly decreased than that of fish oil group. The results suggested that supplementation with fish oil mainly affected the activation of AC, not β-adrenoceptor itself.展开更多
A small shielding effect on the hydrogen atoms of chiral carbons of β-cyclodextrin (β-CD) was detected by 1H nuclear magnetic resonance, but a large environmental change of the chiral carbon atoms at high concentr...A small shielding effect on the hydrogen atoms of chiral carbons of β-cyclodextrin (β-CD) was detected by 1H nuclear magnetic resonance, but a large environmental change of the chiral carbon atoms at high concentration ratios of lithium carbonate (Li2CO3) to β-CD was observed by polarimetry in aqueous solution. These findings urged us to investigate whether different formation conditions of the molecule-ion system between Li2CO3 and β-CD in solid state were involved in different spectral performances. To answer the question, we prepared three adducts of Li2CO3 to β-CD, i.e., samples 1, 2, and 3, by magnetic stirring, solvothermal and grinding conditions, respectively. Powder X-ray diffraction and Fourier transformation infrared spectroscopy provided the information of formation of the three molecule-ion adducts. Besides, scanning electron microscope images provided different surface information of the three adducts. Further, significant spectral differences in thermal behavior of these adducts were found by thermogravimetry and derivative thermogravimetry.展开更多
To improve the covalent immobilization of penicillin acylase (PA), macromolecular crowding theory was applied to its immobilization. Influence of mass ratio of enzyme to the silica, as well as, activation time with ...To improve the covalent immobilization of penicillin acylase (PA), macromolecular crowding theory was applied to its immobilization. Influence of mass ratio of enzyme to the silica, as well as, activation time with glutaraldehyde on the activity of assembled PA, was studied. In the mesopores, the effect of fl-cyclodextrin (β-CD) on the immobilization of the enzyme was also investigated. It was remarkable that the coupled yield and relative activity reached 99.5% and 92.3%, respectively, when penicillin acylase assembled covalently in the mesopores. The results here indicate that mimicked macromolecule crowding could significantly ameliorate the performance of covalently immobilized PA.展开更多
The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. I...The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.展开更多
基金supported by the National Natural Science Foundation of China (21425627,21376279)~~
文摘Nineβ‐cyclodextrin derivatives containing an amino group were synthesized via nucleophilic sub‐stitution from mono(6‐O‐p‐tolylsulfonyl)‐β‐cyclodextrin and used in asymmetric biomimetic Mi‐chael addition reactions in water at room temperature. The mechanism responsible for the moder‐ate activity and enantioselectivity of the β‐cyclodextrin derivatives was explored using nuclear magnetic resonance spectroscopy, namely 2D 1H rotating‐frame overhauser effect spectroscopy (ROESY), ultraviolet absorption spectroscopy, and quantum chemical calculations, which provide a useful technique for investigating the formation of inclusion complexes. The effects of the pH of the reaction medium, theβ‐cyclodextrin derivative dosage, the structure of the modifying amino group, and various substrates on the yield and enantioselectivity were investigated. The results indicated that these factors had an important effect on the enantiomeric excess (ee) in the reaction system. Experiments using a competitor for inclusion complex formation showed that a hydrophobic cavity is necessary for enantioselective Michael addition. A comparison of the reactions using 4‐nitro‐β‐nitrostyrene and 2‐nitro‐β‐nitrostyrene showed that steric hindrance improved the enan‐tioselectivity. This was verified by the optimized geometries obtained from quantum chemical cal‐culations. An ee of 71%was obtained in the asymmetric Michael addition of cyclohexanone and 2‐nitro‐β‐nitrostyrene, using (S)‐2‐aminomethylpyrrolidine‐modified β‐CD as the catalyst, in an aqueous buffer solution, i.e., CH3COONa‐HCl (pH 7.5).
文摘Aim To prepare and characterize the QURC-HP-β-CD inclusion complexes and investigate the thermodynamic parameters of the process. Methods QURC-HP-β-CD inclusion complexes were prepared by the grinding method. The equilibrium inclusion constants and thermodynamic parameters were determinated by phase solubility analysis. Dissolution tests were performed to study the dissolution rate of inclusion complexes. The formation of inclusion complexes was confirmed by differential scanning calorimetry ( DSC), infrared spectroscopy (IR) , powder X-ray diffractometry (PXRD) and scanning electron microscopy (SEM). Results The aqueous solubility of quercetin was greatly increased ( about 37 folds) by inclusion technique, and the initial dissolution rate was markedly improved (10 folds) in the first 5 min. The results of DSC and SEM photographs showed that quercetin crystal disappeared in inclusion complexes, which indicated the formation of new phase. FT-IR spectra showed that the carbonyl quercetin crystal grinding method. absorption band of quercetin was shifted. PXRD showed that the diffraction peak of disappeared. Conclusion QURC-HP-β-CD inclusion complexes are produced by the The solubility of quercetin is improved by the inclusion technique.
基金Project(21001041) supported by the National Natural Science Foundation of ChinaProject(102300410256) supported by Henan Province Foundation and Advanced Technology Research Program,China+1 种基金Project(102102210183) supported by the Key Scientific and Technological Research Project of Henan Province,ChinaProject(2011B480005) supported by the Natural Science Research Project of Henan Province,China
文摘With LiAc-2H2O as Li precursor,pure olivine phase LiFePO4/C was synthesized at a relatively low temperature(650 ℃) and short sintering period(4 h) by molten salt carbothermal reduction method.Scanning electron micrograph shows that particle size of the product is about 1μm,smaller than that of the sample synthesized with Li2CO3 as Li precursor.Electrochemical measurements prove that LiFePO4/C obtained from LiAc-2H2O shows high capacity.The initial discharge capacities are 148 mA-h/g at 0.5C rate and 115 mA-h/g at 5C rate,respectively.After 50 cycles,the capacity retention ratios are 93% and 89% at 0.5C rate and 5C rate,respectively.
基金Supported by Special Fund for Agro-scientific Research in the Public Interest of China(201003073)Key Laboratory Program of Agriculture Ministry of China(2013JCYJ-004)+1 种基金Applied Basic Research Program of Chengdu City Science and Technology Bureau(11DXYB039NC)Youth Foundation of Sichuan Province(2011QNJJ-010)~~
文摘ObjectiveThe study aimed to explore the factors regulating carotenoid accumulation in flesh color. MethodA loquat mutation (red-or orange-fleshed plant emerged a bud mutation of white-flesh in trunk) was used as material; HPLC analysis of β-carotene content was conducted. ResultThe β-carotene concentration in the flesh of wild and mutant types was 60.9 and 4.6 μg/g fresh weight, respectively. According to the conserved regions of genes from rose family genome, carotenogenic gene fragments in wild and mutant types were obtained. No nucleotide variation of the carotenogenic gene fragments was observed between wild and mutant genome. Real-time quantitative polymerase chain reaction (Q-PCR) was compared and one carotenogenic gene, β-ring hydroxylase (HYB) were considerably suppressed in mature mutant loquat fruits compared with that in wild. The other six carotenogenic genes were also expressed but the expression patterns appeared to be not correlated with the amount of β-carotene concentration in wild loquat flesh. ConclusionThe mutant whitish loquat lacks the ability to synthesize β-carotene because of the transcriptional down-regulation of carotenogenic gene HYB.
基金supported by the National Natural Science Foundation of China (21376279, 21276102, 21425627)Guangdong Technology Research Center for Synthesis and Separation of Thermosensitive Chemicals (2015B090903061)+1 种基金the Fundamental Research Funds for the Central Universities (14lgpy28)Guangzhou Science and Technology Plan Projects (2014J4100125)~~
文摘We have designed and prepared β-cyclodextrin (β-CD)-functionalized multi-walled nanotubes (MWCNTs-g-CD) for the oxidation of cinnamon oil to natural benzaldehyde under aqueous condi- tions. The synergistic effect of combining MWCNTs with β-CD led to a remarkable increase in the performance of the MWCNTs-g-CD for the catalytic oxidation of cinnamaldehyde, which exhibited 95% cinnamaldehyde conversion and 85% selectivity to natural benzaldehyde with a short reaction time of 10 rain. The MWCNTs-g-CD also exhibited outstanding recyclability with good stability, showing no discernible decrease in their catalytic activity over five reaction cycles.
文摘Aim To investigate the combined effect of hydroxypropyl-β-cyclodextrin (HP-β-CD) and media pH on the solubility of prostaglandin E1 (PGE1) and construct a theoretical equation for the drug solubility as a function of HP-β-CD concentration and media pH. Methods The solubility of PGE1 under different pH conditions was determined. Then, the drug solubility in different concentrations of HP-β-CD acidic or pH neutral solutions was measured, respectively. Finally, a theoretical solubility equation for the drug as a function of HP-β-CD concentration and media pH was deduced and confirmed in experiment. Results PGEs was solubilized by HP-β-CD or by increasing media pH. The drug solubility as a function of HP-β-CD concentration was found to follow the AL-type complexation model in acidic or neutral pH media, suggesting that both the ionized and neutral drugs form 1:1 molecular ratio complexes. Conclusions The solubility of PGE1 may be improved by increasing media pH or by using HP-β-CD as a solubilizer. HP-β-CD and media pH can produce combined effect on the solubility of PGE1. The deduced equation for the drug solubility in this study effectively characterizes the roles of HP-β-CD and media pH in determining total solubility of the drug.
文摘A new capillary gas chromatography stationary phase, monokis (2,6 di O benzyl 3 O propyl (3’)) hexakis(2,6 di O benzyl 3 O methyl) β CD bonded polysiloxane, was synthesized. It exhibited separation abilities to disubstituted benzene isomers and some chiral solutes. It was also found that the polarity of CD derivatives can be lowered both by chemically bonding it to polysiloxane and by diluting it in polysiloxane. The separation abilities of the polysiloxane anchored CDs (SP CD) are higher than that of the unbonded CDs (S CD) and the diluted S CD at lower column temperature. Hydrosilylation reaction is one of the best methods to lower the operating temperature of CDs.
文摘Some homological properties of R-modules were investigated by matrices over aring R. Given two cardinal numbers α, β and an α x β row-finite matrix A, it was proved thatExt_R^1(R^((α))/R^((β))A, M) = 0 if and only if M_α/r_(M_α)(R^((β))A) ≈ Hom_R(R^((β))A,M) ifand only if r_(M_β)l_(R^((β)))(A) = AM_α. Thus, the notion of (m,n)-injectivity was extended.Moreover, ( α, β) -flatness was characterized via annihilators of matrices, factorizations ofhomomorphisms as well as homological groups so that (m, n)-flat modules, f-projective modules andn-projective modules were consolidated under the notion of (α, β)-flat modules. Furthermore, acharacterization of left R-ML modules and some equivalent conditions for R^((β)) to be left R-MLwere presented. Consequently, the notions of coherent rings, (m, n)-coherent rings and π-coherentrings were consolidated under that of (α, β)-coherent rings.
文摘Effects of fish oil on β-adrenoceptors as well as the activity of adenylate cyclase (AC) on rat myocardial membrane were investigated.Supplementation with fish oil had no significant effect on basal activity of AC on myocardial membrane whereas it could markedly inhibit the AC activity stimulated by isoproterenol (ISO). Radioligand binding assays showed that supplementation with fish oil had no effect on Bmax and Kd, compared with saline control. However, supplementation with sheep oil could markedly reduce both the Kd and Bmax, compared with saline control. And the Kd of sheep oil group was greatly decreased than that of fish oil group. The results suggested that supplementation with fish oil mainly affected the activation of AC, not β-adrenoceptor itself.
基金ACKNOWLEDGMENTS This work was supported by the Innovation Foundation of Graduate Students in University of Science and Technology of China (No.KD2008020), and the Natural Science Foundation of Anhui Province (No.090416228).
文摘A small shielding effect on the hydrogen atoms of chiral carbons of β-cyclodextrin (β-CD) was detected by 1H nuclear magnetic resonance, but a large environmental change of the chiral carbon atoms at high concentration ratios of lithium carbonate (Li2CO3) to β-CD was observed by polarimetry in aqueous solution. These findings urged us to investigate whether different formation conditions of the molecule-ion system between Li2CO3 and β-CD in solid state were involved in different spectral performances. To answer the question, we prepared three adducts of Li2CO3 to β-CD, i.e., samples 1, 2, and 3, by magnetic stirring, solvothermal and grinding conditions, respectively. Powder X-ray diffraction and Fourier transformation infrared spectroscopy provided the information of formation of the three molecule-ion adducts. Besides, scanning electron microscope images provided different surface information of the three adducts. Further, significant spectral differences in thermal behavior of these adducts were found by thermogravimetry and derivative thermogravimetry.
基金Supported by the National High Technology Research and Development Program of China (863 Program, No.2006AA02Z211), the National Natural Science Foundation of China (No.20376034), the Natural Science Foundation of Jiangsu Province of China (BK2006181), and the Scientific Research Foundation for Young Teachers in the Higher Education Institutions of Anhui Province of China (2005jq1163), and the Foundation of Jiangsu Province of China for College Postgraduate Students in Inno-vation Engineering (2007).
文摘To improve the covalent immobilization of penicillin acylase (PA), macromolecular crowding theory was applied to its immobilization. Influence of mass ratio of enzyme to the silica, as well as, activation time with glutaraldehyde on the activity of assembled PA, was studied. In the mesopores, the effect of fl-cyclodextrin (β-CD) on the immobilization of the enzyme was also investigated. It was remarkable that the coupled yield and relative activity reached 99.5% and 92.3%, respectively, when penicillin acylase assembled covalently in the mesopores. The results here indicate that mimicked macromolecule crowding could significantly ameliorate the performance of covalently immobilized PA.
文摘The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.